System for reducing NOx in exhaust

ABSTRACT

A system and method for NOx reduction is described, with a catalytic unit including a first zeolite catalyst with a first NOx conversion performance in a first temperature range and a second NOx conversion performance, lower than said first NOx conversion performance, in a second temperature range. The catalytic unit also comprises a second zeolite catalyst with a third NOx conversion performance, lower than said first NOx conversion performance, in the first temperature range and a fourth NOx conversion performance, higher than said second and third NOx conversion performances in the second temperature range, said first temperature range being higher than said second temperature range. The system further includes a controller configured to adjust an amount of reducing agent added to the NOx reducing system responsive to a temperature of the catalytic unit.

FIELD

The present description relates generally to an exhaust treatment systemfor a combustion engine.

BACKGROUND/SUMMARY

Nitrogen oxides, such as NO and NO₂ (collectively referred to as NOx),generated in the high temperature and high pressure conditions of aninternal combustion engine, may constitute a large percentage of totalexhaust emissions. Accordingly, engine exhaust systems may utilizeselective catalytic reduction (SCR) to reduce the NOx species todiatomic nitrogen and water.

A variety of SCR catalysts have been developed including base metalcatalysts and zeolite catalysts. However, the inventors herein haverecognized several issues with such catalysts. Specifically, thecatalysts may have limited operating temperature ranges, varying thermaldurability, and may suffer from ammonia slip. As one example,copper-exchanged zeolites may efficiently reduce NOx at lowertemperatures. However, at higher temperatures, they may oxidize thereducing agent leading to poor NOx conversion.

In one example, some of the above issues may be addressed by a systemfor a vehicle including an engine having an exhaust, the systemcomprising a NOx reducing system coupled to the engine exhaust. The NOxreducing system may include a catalytic unit with a first zeolitecatalyst with a first NOx conversion performance in a first temperaturerange and a second NOx conversion performance, lower than said first NOxconversion performance, in a second temperature range. The catalyticunit may also include a second zeolite catalyst with a third NOxconversion performance, lower than said first NOx conversionperformance, in the first temperature range and a fourth NOx conversionperformance, higher than said second and third NOx conversionperformances in the second temperature range, said first temperaturerange being higher than said second temperature range. The system mayfurther comprise a controller configured to adjust an amount of reducingagent added to the NOx reducing system responsive to a temperature ofthe catalytic unit.

In one example, the catalytic unit may include a first Fe-exchangedzeolite catalyst with a (first) higher NOx conversion performance in thefirst higher temperature range. However, in a second lower temperaturerange, the Fe-exchanged zeolite catalyst may have a (second)substantially lower performance. The catalytic unit may also include asecond Cu-exchanged zeolite catalyst with a (third) lower performance inthe aforementioned higher temperature range, but may be configured tohave a (fourth) higher performance in the aforementioned lowertemperature range. In other words, the first zeolite catalyst may beconfigured with a higher optimal operating temperature range while thesecond zeolite catalyst may be configured with a lower optimal operatingtemperature range.

In this way, by combining catalysts with differing NOx conversionperformances in differing operating temperature ranges, and by adjustingreducing agent delivery responsive to catalyst temperature, a catalystcombination with a substantially broader operating temperature range anda significantly improved NOx conversion performance over that broadoperating temperature range may be generated. By using such an improvedcatalyst combination in a NOx reducing system, the quality of exhaustemissions may be improved. Further, by adjusting an amount of reducingagent delivered, for example by increasing reducing agent delivery athigher temperatures, increased NOx performance over the broadertemperature range can be achieved.

It should be understood that the summary above is provided to introducein simplified form a selection of concepts that are further described inthe detailed description. It is not meant to identify key or essentialfeatures of the claimed subject matter, the scope of which is defineduniquely by the claims that follow the detailed description.Furthermore, the claimed subject matter is not limited toimplementations that solve any disadvantages noted above or in any partof this disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a schematic depiction of an engine and an associated NOxreducing system.

FIG. 2 shows an embodiment of the NOx reducing system of FIG. 1.

FIG. 3A shows a graphical comparison of NOx conversion performances as afunction of catalyst temperature for a gas flow treated over acopper-zeolite catalyst versus a copper-zeolite/iron zeolite combinationcatalyst of the NOx reducing system of FIG. 2.

FIG. 3B shows a graphical comparison of the NOx conversion performanceof the copper-zeolite/iron zeolite catalyst combination at a fixed alphavalue versus a temperature-dependent alpha value.

FIG. 4 shows a high level flow chart for NOx reduction in the NOxreducing system of FIG. 2.

FIG. 5 shows a high level flow chart for generating thetemperature-dependent alpha curve of FIG. 3B.

DETAILED DESCRIPTION

The following description relates to systems and methods for optimizingNOx reduction in a NOx reducing system coupled to an engine exhaust, asshown in FIG. 1. In one example, a zeolite-based NOx reducing systemincluding a combination of different zeolite catalysts may be used, asshown in FIG. 2. The zeolites may be staged in the NOx reducing systemsuch that the majority of benefits of each individual zeolite catalystmay be taken advantage of, and additional synergistic benefits may alsobe achieved. As shown in FIGS. 3A-B, the reducing capability of thecatalyst combination may be further enhanced by adjusting the amount ofreducing agent (for example, ammonia) added to the NOx reducing systemso as to vary an alpha value (that is, a ratio of the reducing agent toNOx species) responsive to a temperature of the NOx reducing system.FIGS. 4-5 describe routines enabling the mentioned temperature-dependentalpha value adjustment. Thus, by combining different zeolite catalystswith differing characteristics, an improved NOx reducing system may beformed. By further adjusting an amount of reducing agent addedresponsive to the temperature of the NOx reducing system, or a componentthereof, such as the catalytic unit, the overall NOx conversionperformance of the catalysts may be further enhanced. In this way, thequality of exhaust emissions may be significantly improved.

FIG. 1 shows a schematic depiction of a vehicle system 6. The vehiclesystem 6 includes an engine system 8 coupled to a NOx reducing system22. The engine system 8 may include an engine 10 having a plurality ofcylinders 30. The engine 10 includes an engine intake 23 and an engineexhaust 25. The engine intake 23 includes a throttle 62 fluidly coupledto the engine intake manifold 44 via an intake passage 42. The engineexhaust 25 includes an exhaust manifold 48 leading to an exhaust passage35 that routes exhaust gas to the atmosphere. The engine exhaust 25 mayinclude one or more emission control devices, which may be mounted in aclose-coupled position in the exhaust. The one or more emission controldevices may include NOx reducing system 22. Additional emission controldevices (not shown) may include a three-way catalyst, a dieselparticulate filter, oxidation catalyst, etc. It will be appreciated thatother components may be included in the engine such as a variety ofvalves and sensors.

NOx reducing system 22 may include a plurality of zeolite-basedcatalysts, as further elaborated in FIG. 2, to perform a selectivecatalytic reduction (SCR) of the NOx species of an exhaust entering thesystem. Specifically, the catalysts promote the reaction of a reducingagent 64, such as ammonia, with nitrogen oxides (NOx) to form nitrogenand water selectively over the competing reaction of oxygen and thereducing agent. The NOx reducing system may include a first zeolitecatalyst with a first NOx conversion performance in a first temperaturerange and a second NOx conversion performance, lower than said first NOxconversion performance, in a second temperature range. The system mayalso include a second zeolite catalyst with a third NOx conversionperformance, lower than said first NOx conversion performance, in thefirst temperature range and a fourth NOx conversion performance, higherthan said second and third NOx conversion performances, in the secondtemperature range. As such, the first temperature range may be higherthan the second temperature range. Further details regarding thecomposition and configuration of NOx reducing system 22 is elaboratedbelow with reference to FIG. 2.

Reducing agent 64 may be added to the exhaust gas just before it entersNOx reducing system 22. The liquid reducing agent 64 may be injectedinto the exhaust by reducing agent injector 68, in an atomized or mistform 72, in response to a signal from an engine control system. Thereducing agent may be stored in reducing agent tank 20. A valve (notshown) and/or a pump (not shown) may be used to control flow andpressure of the reducing agent into injector 68.

In one example, reducing agent 64 may be anhydrous or aqueous ammonia.While it may be desirable to provide ammonia in excess of thestoichiometric amount required to react completely with the nitrogenoxides present and drive the reaction to completion, the discharge ofthe excess unreacted ammonia (known as ammonia slip) may itself degradeemissions quality. Thus, in one example, ammonia may be added in anamount to provide an ammonia to NOx ratio (or alpha value) ranging from0.5 to 2.0 moles of ammonia per mole of NOx. Other alpha value rangesmay be similarly configured responsive to a desired operatingtemperature and the composition of the catalysts in the NOx reducingsystem. Even during reaction in the presence of stoichiometric orsub-stoichiometric levels of reducing agent, ammonia slip may occur dueto incomplete mixing of the reducing agent with the catalyst. Inalternate embodiments, the reducing agent may be any other ammoniagenicagent. As such, ammoniagenic agents may be capable of generating ammoniaunder specified conditions. As one example, the ammoniagenic agent mayinclude aqueous urea or ammonia.

A fuel system (not shown) may be provided including one or more pumpsfor pressurizing fuel delivered to the injectors of engine 10, such asthe example injector 66 shown. While only a single injector 66 is shown,additional injectors may be provided for each cylinder. The fuel systemmay be a return-less fuel system, a return fuel system, or various othertypes of fuel system.

The vehicle system 6 may further include control system 14. Controlsystem 14 is shown receiving information from a plurality of sensors 16and sending control signals to a plurality of actuators 81. As oneexample, sensors 16 may include exhaust gas sensor 126 located upstreamof the emission control device. Other sensors such as pressure,temperature, air/fuel ratio, and composition sensors may be coupled tovarious locations in the vehicle system 6. As another example, theactuators may include fuel injector 66, reducing agent injector 68, andthrottle 62. The control system 14 may include a controller 12. Thecontroller may receive input data from the various sensors, process theinput data, and trigger the actuators in response to the processed inputdata based on instruction or code programmed therein corresponding toone or more routines. Example control routines are described herein withregard to FIGS. 4-5.

A temperature sensor (not shown) may be coupled to the NOx reducingsystem to monitor a temperature of the system. The temperature may thenbe communicated with the engine control system. As further elaborated inFIGS. 3B-5, an amount of reducing agent added to the NOx reducing systemmay be adjusted responsive to the temperature of the catalytic unit ofthe NOx reducing system to augment the NOx reducing efficiency of theincluded zeolite catalysts.

Referring now to FIG. 2, one embodiment 200 of NOx reducing system 22 isdescribed. Untreated exhaust 220 is directed from the engine into NOxreducing system 22, comprising catalytic unit 222, along exhaust passage35. The untreated exhaust 220 from the engine, in the form of a gasstream (represented by an arrow), is conducted into the catalytic unit222 along inlet port 204 in the direction indicated by the arrow. In thedepicted embodiment, the NOx reducing catalytic unit 222 is housedinside an airtight housing 202, which thereby defines a packing volumeoccupied by the catalytic unit. Following catalytic treatment in thecatalytic unit, treated exhaust gas 224 may be discharged along outletport 206 into exhaust passage 35, for subsequent venting to theatmosphere.

Catalytic unit 222 may include a first zeolite catalyst 210 and a secondzeolite catalyst 212. The first and second zeolite catalysts 210 and 212may be juxtaposed next to one another. Alternatively, as depicted, thefirst and second zeolite catalysts may be spaced apart at a distance 214from each other. In either case, the first zeolite catalyst 210 may belocated between the inlet port 204 of the NOx reducing system and thesecond zeolite catalyst 212; while second zeolite catalyst 212 may belocated between the first zeolite catalyst 210 and the outlet port 206of the NOx reducing system. Further, the first and second zeolitecatalysts may be supported by a substrate support. Alternatively, one ormore of the first and second zeolite catalysts may be included in thesubstrate support.

While the depicted embodiment shows the two catalysts in a stagedconfiguration, in alternate embodiments, the two catalysts may be in alayered configuration with the first zeolite catalyst forming an upperlayer, and the second zeolite catalyst forming a lower layer. Herein,the second zeolite catalyst may be coated on the substrate support toform the lower layer while the first zeolite catalyst may be coated onthe lower layer to form the upper layer.

As such, various embodiments may be possible when using the substratesupport with the zeolite catalysts. Further variations may be possiblewhen using various substrate supports. In some embodiments, thesubstrate support may have a high porosity of 30 to 95%. Further, thehigh porosity substrate support may be extruded. The extruded supportmay be catalytically active or non-active for the desired SCR chemicalreaction. In still other embodiments, the substrate support may comprisea diesel particulate filter (DPF). The DPF substrate support may includea plurality of channels with alternating ends blocked. By using a DPFsubstrate support, particulate matter trapping, particulate matterburn-off and NOx reduction may occur simultaneously. Various othersuitable particulate filters may alternatively be used.

In one example, the first zeolite catalyst may be included at the outeredge of the substrate support (for example, the high porosity substratesupport) while the second zeolite catalyst may be included in the centerof the substrate support. In another example, the second zeolitecatalyst may be included within the substrate support while the firstzeolite catalyst may be coated on top of the second catalyst. In thisway, the first and second zeolite catalysts with differing optimaloperating temperature ranges, may be used advantageously in a widevariety of configurations.

It will be appreciated that the first zeolite catalyst and secondzeolite catalyst herein also refer to the sequence in which thecatalysts may be introduced to untreated exhaust gas. Thus, the firstzeolite catalyst 210 is also an upstream catalyst, located upstream ofthe second zeolite catalyst while the second zeolite catalyst 212 isalso a downstream catalyst, located downstream of the first zeolitecatalyst. It will also be appreciated that herein the terms upstream anddownstream may be as sensed in the direction of untreated exhaustflowing through the catalytic unit 222 before being vented to theatmosphere.

In one embodiment, both the first and second zeolite catalysts may bemetal-exchanged zeolites. Specifically, both catalysts may be transitionmetal-exchanged zeolite catalysts. The base zeolite may have a highsilica to alumina molar ratio, such as mordenite for example. The highsilica to alumina ratio may impart temperature stability to the zeoliteand may also increase resistance to sulfurous poisons. The temperaturestable base zeolite may further ensure a positive influence on the agingcharacteristics of the catalysts. The base zeolite may be ion-exchangedwith metals such as iron (Fe) or copper (Cu) to generate themetal-exchanged zeolites. As one example, (in the embodiment depictedwith respect to FIGS. 3A-B) the first zeolite catalyst 210 may be anFe-exchanged zeolite catalyst while the second zeolite catalyst 212 maybe a Cu-exchanged zeolite catalyst. In alternate examples, vanadium,cobalt, nickel, chromium, or other appropriate metals may be used. Assuch, the exchanged metal may include the elemental metal itself and/orthe metal oxide.

First zeolite catalyst 210 may have a first NOx conversion performancein a first temperature range and a second NOx conversion performance,lower than said first NOx conversion performance, in a secondtemperature range. Second zeolite catalyst 212 may have a third NOxconversion performance, lower than said first NOx conversionperformance, in the first temperature range and a fourth NOx conversionperformance, higher than said second and third NOx conversionperformances in the second temperature range. As such, the firsttemperature range may be higher than said second temperature range. Asone example, when the first zeolite catalyst is an Fe-exchanged zeolitecatalyst and the second zeolite catalyst is a Cu-exchanged zeolitecatalyst, the first catalyst may exhibit a significantly higher NOxconversion performance in a higher temperature range of 450° C. to 600°C., while the second catalyst may exhibit a significantly higher NOxconversion performance in a lower temperature range of 200° C. to 400°C. That is, in the upper temperature range the Fe-exchanged zeolite maybe primarily responsible for reduction of the NOx species, while in thelower temperature range the Cu-exchanged zeolite may be primarilyresponsible for reduction of the NOx species.

While the example illustrates non-overlapping temperature ranges, inalternate embodiments, the temperature ranges may be partiallyoverlapping. Herein, by placing the first zeolite catalyst with thehigher performance at the higher temperature range in front of thesecond zeolite catalyst with the higher performance at the lowertemperature range, the second catalyst may be buffered by the firstcatalyst against high temperature exhaust gas entering the catalyticunit 222. In this way, the second zeolite catalyst may be buffered fromhot exhaust gas by the first zeolite catalyst and detrimental effects ofthe hot exhaust gas on the second catalyst may be averted.

As such, by themselves, Cu-exchanged zeolite catalysts may be moreactive at lower temperature ranges and thus may be desirable for usewhen the exhaust gas temperature is below 400° C., for example. However,at higher temperature ranges, Cu-exchanged zeolite catalysts may tend toselectively oxidize the reducing agent, for example ammonia, tonitrogen. The resultant drop in ammonia concentration may then adverselyaffect the catalytic efficiency of the Cu-exchanged zeolite catalyst. Incontrast, by themselves, Fe-exchanged zeolite catalysts may be moreactive at higher temperature ranges, efficiently converting NOx speciesat temperatures above 450° C., and even as high as 600° C. However, atlower temperatures, particularly in the absence of any NO₂ species,their efficiency may drop significantly. Further, the Fe-exchangedzeolite catalysts may suffer from ammonia slip. Nonetheless, when thedifferent zeolite catalysts are combined, as claimed herein, thetemperature range of the catalytic unit over which significant NOxreduction may occur can be substantially broadened, as furtherillustrated with respect to FIG. 3A. For example, upon combination, thecatalytic unit may operate in a temperature range stretching from about200° C. to 600° C. Specifically, in the lower temperature range, whenthe Fe-exchanged zeolite catalyst is substantially inactivated, theCu-exchanged zeolite catalyst may be activated to reduce NOx species,while in the higher temperature range, when the Cu-exchanged zeolitecatalyst is substantially inactivated, the Fe-exchanged zeolite catalystmay be activated and may take over the function of reducing NOx species.A lower threshold of the combination catalyst temperature range may below enough to efficiently reduce exhaust from diesel engines, while anupper threshold of the temperature range may be high enough toefficiently reduce exhaust from gasoline-based engines. Additionalsynergistic benefits may also be achieved by combining the differentmetal-exchanged zeolite catalysts. As one example, the catalystcombination may not suffer from ammonia slip, even when overdosed withammonia.

The Fe-exchanged and/or Cu-exchanged zeolite catalysts of the presentdisclosure may be generated by layering catalyst coatings on a substratesupport. The iron and/or copper containing zeolite catalysts may beground to a fine powder for generating the catalyst coatings in slurryform. The catalytic coatings may then be applied to structurereinforcing carriers made of refractory ceramic material such ascorderite, mullite or alumina. Alternatively, the carrier may be made ofmetallic foil, silicon carbide, etc. The carriers may also be highporosity substrate supports, with a porosity ranging between 30 to 95%.In one example, the substrate support may be high porosity cordierite.Further still, the carriers may be in monolith or honeycomb form.

The ratio of the first and second zeolite catalyst in the catalytic unitmay be adjusted based on a desired SCR performance level, as well as adesired operating temperature range for the catalytic unit. In oneexample embodiment, a molar ratio of the first (Fe-exchanged) zeolitecatalyst to the second (Cu-exchanged) zeolite catalyst may be 1:2. Inalternate examples, the zeolite catalysts may be in equal molar ratiosor with twice as much Fe-exchanged zeolite catalyst as Cu-exchangedzeolite catalyst. Still other combinations may be possible. As such, thecopper content of the (second) zeolite catalyst may be in the range of0.1 to 10.0% by weight while the iron content of the (first) zeolitecatalyst may be in the range of 0.1 to 10.0% by weight.

To further enhance the performance of the combination catalyst, a ratioof the amount of reducing agent added to the amount of NOx speciespresent, for example a ratio of ammonia to NOx species (herein alsoreferred to as an alpha value), may be adjusted to a desired ratio. Thedesired ratio may be determined based on various factors to optimize theperformance of the catalytic unit. As illustrated and elaborated below,with reference to FIGS. 3B-5, the alpha value may be adjusted responsiveto a temperature of the catalytic unit of the NOx reducing system, tothereby augment the NOx reduction efficiency of the catalytic unit.

In this way, by combining metal-exchanged zeolite catalysts of differingperformance characteristics, and differing NOx reduction efficiencies atdiffering temperature ranges, a NOx reducing catalytic unit ofsubstantially broader operating temperature range may be generated. Bycovering a broader range, engine exhaust generated from a wide varietyof fuels may be treated effectively. Further, the combined system mayprovide additional benefits that may not be achieved by either catalystalone, such as higher overall resistance to sulfurous poisons, highertolerance to overdosing of reducing agent, and negligible ammonia slip.

FIG. 3A shows a map 300 a graphically comparing NOx conversionperformances of the catalyst combination of the present disclosureversus a copper-exchanged zeolite catalyst, over a wide range oftemperatures. The catalyst combination tested herein has a blend of acopper-exchanged zeolite and an iron-exchanged zeolite at a molar ratioof 2:1. The catalyst temperature is plotted along the x-axis while theNOx conversion performance is plotted (as a percentage) on the y-axis.

Simulated gas treatment tests were performed in the furnace of a flowreactor. For ease of experimentation, only NO was used as therepresentative NOx species. The conditions under which the tests wereperformed included an inlet gas blend of 14% oxygen (O₂), 5% water(H₂O), 5% carbon dioxide (CO₂), 350 ppm NO, 350 ppm ammonia (NH₃) andthe balance nitrogen. Gas was blended in a first furnace while thecatalyst core was housed in a second (connected) furnace. Ammonia wasadded to the hot gas mixture at the inlet of the second furnace. Thecatalyst formulations were coated on 400/4.5 CPSI cordierite substrates.The catalysts were first heat aged for 64 hours at 670° C. The catalystsubstrates were then tested at a space velocity of 90,000 hr⁻¹ with aflow of 9.66 SLM. The catalyst core temperature was varied between 150°C. and 600° C., in a controlled manner. Following reaction, the gasmixture components were analyzed by Fourier transform infra-redspectroscopy (FTIR) analysis.

As shown in FIG. 3A, at lower temperature ranges (such as, ˜150° C. to˜250° C.), the NOx conversion curve 302 (solid line) for thecopper-based zeolite catalyst and the NOx conversion curve 304 (dashedline) for the catalyst combination exhibit similar trends. However, asthe temperature of the catalyst is raised, a significant differencebetween their performances may be visible. In particular, the differencein performance between the catalysts may increase from ˜5% at 300° C. to˜40% at 600° C., with the catalyst combination substantiallyout-performing the copper-exchanged zeolite catalyst. Thus, while athigher temperature ranges the copper-exchanged zeolite catalyst suffersfrom heat inactivation and oxidation of ammonia, in the combinationcatalyst, this drawback is overcome by the presence of theiron-exchanged zeolite catalyst that takes over NOx reduction as thetemperature increases. It will be appreciated that similar results (notshown) may be obtained when comparing the performance of the combinationcatalyst with an iron-exchanged zeolite catalyst with the combinationcatalyst substantially out-performing the Fe-exchanged zeolite catalystat lower temperature ranges.

To further enhance the performance of the catalyst combination, theratio of ammonia (the reducing agent) to NOx may be further adjustedresponsive to a temperature of the catalytic unit of the NOx reducingsystem. Specifically, the amount of ammonia added to the NOx reducingsystem may be increased as a temperature of the catalytic unitincreases. In some embodiments, the temperature-dependent adjustment maybe performed such that when the temperature of the catalytic unit is ina first higher temperature range, the amount of reducing agent added tothe NOx reducing system may be increased at a first higher rate. Incontrast, when the temperature of the catalytic unit is in a secondlower temperature range, the amount of reducing agent added to the NOxreducing system may be increased at a second lower rate. Thus, thetemperature-dependent alpha value may be increased with temperature atleast in a range of temperatures. For example, the alpha value may beincreased with temperature in some temperature ranges (such as at hightemperatures) and may not be increased with temperature in othertemperature ranges (such as low temperatures). In the example embodimentdepicted herein, the amount of ammonia added to the NOx reducing systemmay be varied at differing rates responsive to the temperature of theNOx reducing system, to provide an alpha value ranging between 0.5 to2.0 moles of ammonia per mole of NOx. By adjusting the amount of ammoniaadded responsive to the temperature of the catalytic unit, the NOxconversion reaction may be driven to completion by allowing propermixing of the nitric oxides with ammonia, without causing ammonia slip.A control system of the engine may be configured to adjust the amount ofammonia added by performing an alpha value adjustment routine 500, asdetailed in FIG. 5.

FIG. 3B shows a map 300 b graphically comparing NOx conversionefficiencies of the catalyst combination at either a fixed alpha value,or with an adjusted alpha value, over a wide range of operatingtemperatures. As such, the adjustment to the alpha value may beperformed in a temperature-dependent manner. The temperature of thecatalyst combination is depicted along the x-axis while the NOxconversion efficiency is plotted (as a percentage) on the primaryy-axis. The alpha value is plotted on the secondary y-axis.

The simulated gas treatment tests were performed as previouslyelaborated with respect to FIG. 3A. NO was used as the representativeNOx species and was introduced at a concentration of 350 ppm. Whenvarying the alpha value, the ammonia concentration was adjusted withrespect to the NO concentration to generate an alpha value ranging from0.7 (245 ppm NH₃) to 2.0 (700 ppm NH₃). When using a fixed value, thealpha value was set at 1.0 (350 ppm NH₃).

Map 300 b shows a first NOx conversion curve 306 of the combinedcatalyst wherein the alpha value remains fixed at a value of 1.0, asindicated by fixed alpha curve 308. A second NOx conversion curve 310for the same combination catalyst is also depicted wherein the alphavalue is increased responsive to the temperature of the catalytic unit,as shown by temperature-dependent alpha curve 312. Specifically, thealpha value, and consequently the amount of reducing agent (hereinammonia) added to the NOx reducing system, is increased at differentrates responsive to the temperature. In particular, the amount ofammonia added may be increased at different rates in differenttemperature ranges of the catalytic unit. The amount of ammonia added isincreased at a lower rate in a first temperature range comprising lowertemperatures while the amount is increased at a higher rate in a secondtemperature range comprising higher temperatures. While in the depictedembodiment, the temperature-dependent alpha curve follows a non-lineartrend, it will be appreciated that in alternate embodiments, thetemperature-dependent alpha adjustment may follow a linear, or otherappropriate trend.

Comparison of the first NOx conversion curve 306 of the combinedcatalyst in view of fixed alpha curve 308 versus the second NOxconversion curve 310 in view of temperature-dependent alpha curve 312,indicates that towards the lower threshold of operating temperatureranges for the catalyst combination, only in a small temperature range,no substantial difference in NOx reduction can be observed. However, forthe majority of temperatures analyzed, there is a substantial increasein the efficiency of NOx reduction with the temperature-dependent alphacurve. Specifically, when the alpha value is gradually increased as atemperature of the catalyst combination increases in an uppertemperature range, there is an overall enhancement in the already highperformance characteristic of the catalyst combination. As illustrated,when tested at an upper threshold of the operating temperature range(˜600° C.), there may be a significant increase in NOx reduction from˜65% to ˜80%. Thus, by increasing an alpha value responsive to thetemperature of the catalytic unit, the catalytic performance of thecatalytic unit may be augmented.

Given that the Cu-exchanged (second) zeolite catalyst is primarilyresponsible for NOx reduction in the lower temperature range of thecatalytic unit, and the Fe-exchanged (first) zeolite catalyst isprimarily responsible for NOx reduction in the higher temperature rangeof the catalytic unit, the temperature-dependent adjustment of the alphavalue correlates with enhanced performance of the respectiveconstitutive catalysts in their respective operating temperature ranges.As such, independent alpha curves may be generated for the differentzeolite catalysts constituting the combination catalyst in the catalyticunit. However, by using a single temperature-dependent alpha curveresponsive to the operating temperature of the combination catalyst, thehigh cost and complexity involved in customizing the alpha value witheach constitutive catalyst (to thereby achieve overall improved NOxconversion), may be averted.

FIG. 4 depicts an example process flow 400 explaining the NOx reductionprocess in the example NOx reducing system of FIG. 2. At 402, untreatedexhaust gas may be received in the NOx reducing system. At 404, anamount of reducing agent, herein an amount of ammonia, may be injectedinto the NOx reducing system to obtain a desired alpha value. The amountof ammonia added and the desired alpha value may be adjusted responsiveto the temperature of the catalyst combination in the catalytic unit ofthe NOx reducing system. At 406, the NOx species may be reduced by anSCR reaction in the catalytic unit to thereby generate treated exhaustgas.

FIG. 5 depicts an example alpha adjustment routine 400 that may beperformed by a control system of the engine to obtain atemperature-dependent alpha curve as depicted in FIG. 3B. The alphaadjustment enables a desired alpha value to be attained, to therebyoptimize the NOx conversion performance of the combination catalyst inthe NOx reducing system.

At 502, the combination catalyst temperature may be estimated and/ormeasured. The temperature may be estimated by a temperature sensorcoupled to the catalytic unit. Alternatively, the temperature may beinferred from an engine exhaust temperature, or other operatingparameters. At 504, a desired temperature-dependent alpha value (orammonia to NOx ratio) may be determined based on the estimated catalytictemperature. A look-up table may be previously generated and stored in amemory of the engine control system. The look-up table may be configuredto dictate an amount of ammonia (or other reducing agent) to be addedresponsive to the estimated temperature, or temperature range.Accordingly, at 506, an ammonia amount and/or concentration added to thecatalytic unit may be adjusted to obtain the desired alpha value.Specifically, an amount of ammonia added to the NOx reducing system maybe increased as the temperature of the catalyst combination (orcatalytic unit) increases, at least in a range of temperatures, therebyincreasing the alpha value.

As one example, when the catalyst temperature is in a lower temperaturerange (for example, as may occur when receiving exhaust from a dieselfuel), the alpha value may be adjusted to gradually increase at a lowerrate within a sub-stoichiometric range (for example, from 0.5 to 1.0, inparticular from 0.7 to 0.9). In alternate examples, the alpha value mayremain unchanged in the lower temperature range. In another example,when the catalyst temperature is in a higher temperature range (forexample, as may occur when receiving exhaust from a gasoline fuel), thealpha value may be adjusted to gradually increase at a higher rate,within a stoichiometric to above-stoichiometric range (for example, from1.0 to 2.0).

In this way, by increasing the amount of reducing agent added to the NOxreducing system responsive to a temperature of the catalytic unit of aNOx reducing system, the NOx conversion efficiency of the system may beenhanced.

It will be appreciated that the configurations and process flowsdisclosed herein are exemplary in nature, and that these specificembodiments are not to be considered in a limiting sense, becausenumerous variations are possible.

The subject matter of the present disclosure includes all novel andnon-obvious combinations and sub-combinations of the various systems andconfigurations, and other features, functions, and/or propertiesdisclosed herein. The following claims particularly point out certaincombinations and sub-combinations regarded as novel and non-obvious.These claims may refer to “an” element or “a first” element or theequivalent thereof. Such claims should be understood to includeincorporation of one or more such elements, neither requiring norexcluding two or more such elements. Other combinations andsub-combinations of the disclosed features, functions, elements, and/orproperties may be claimed through amendment of the present claims orthrough presentation of new claims in this or a related application.Such claims, whether broader, narrower, equal, or different in scope tothe original claims, also are regarded as included within the subjectmatter of the present disclosure.

1. A system for a vehicle including an engine having an exhaust, thesystem comprising: a NOx reducing system coupled to the engine exhaust,said NOx reducing system including a catalytic unit, said catalytic unitincluding a first zeolite catalyst with a first NOx conversionperformance in a first temperature range and a second NOx conversionperformance, lower than said first NOx conversion performance, in asecond temperature range, and a second zeolite catalyst with a third NOxconversion performance, lower than said first NOx conversionperformance, in the first temperature range and a fourth NOx conversionperformance, higher than said second and said third NOx conversionperformances in the second temperature range, said first temperaturerange being higher than said second temperature range; and a controllerconfigured to adjust an amount of reducing agent added to the NOxreducing system responsive to a temperature of the catalytic unit, theadjusting including increasing the amount of reducing agent added to theNOx reducing system as a temperature of the catalytic unit increases,and when the temperature of the catalytic unit is in the firsttemperature range, increasing the amount of reducing agent added to theNOx reducing system at a first rate, and when the temperature of thecatalytic unit is in the second temperature range, increasing the amountof reducing agent added to the NOx reducing system at a second rate,said first rate being higher than said second rate, the reducing agentbeing an ammoniagenic agent including ammonia or aqueous urea.
 2. Thesystem of claim 1 wherein one or more of the first and second zeolitecatalysts are supported by a substrate support.
 3. The system of claim 1wherein one or more of the first and second zeolite catalysts areincluded in a substrate support.
 4. The system of claim 3 wherein thesubstrate support has a high porosity of 30 to 95%.
 5. The system ofclaim 3 wherein the second zeolite catalyst is included in a center ofthe substrate support and the first zeolite catalyst is included at anouter edge of the substrate support.
 6. The system of claim 3 whereinthe substrate support comprises a diesel particulate filter.
 7. Thesystem of claim 1 wherein the first zeolite catalyst is located betweenan inlet of the NOx reducing system and the second zeolite catalyst, andwhere the second zeolite catalyst is located between the first zeolitecatalyst and an outlet of the NOx reducing system.
 8. The system ofclaim 7 wherein the first and second zeolite catalysts aremetal-exchanged zeolite catalysts.
 9. The system of claim 7 wherein thefirst zeolite catalyst is an iron-exchanged zeolite catalyst and thesecond zeolite catalyst is a copper-exchanged zeolite catalyst.
 10. Thesystem of claim 7 wherein a molar ratio of the first zeolite catalyst tothe second zeolite catalyst is 1:2.
 11. A method of operating a NOxreducing system coupled to an engine exhaust, said NOx reducing systemincluding a catalytic unit, the method comprising: passing engineexhaust gas through the NOx reducing system; and adjusting an amount ofreducing agent added to the NOx reducing system responsive to atemperature of the catalytic unit including a first zeolite catalystwith a first NOx conversion performance in a first temperature range anda second NOx conversion performance, lower than said first NOxconversion performance, in a second temperature range; and a secondzeolite catalyst with a third NOx conversion performance, lower thansaid first NOx conversion performance, in the first temperature rangeand a fourth NOx conversion performance, higher than said second andsaid third NOx conversion performances in the second temperature range,said first temperature range being higher than said second temperaturerange, where adjusting the amount of reducing agent includes: when atemperature of the catalytic unit is in the first temperature range,increasing the amount of reducing agent added to the NOx reducing systemat a first rate; and when the temperature of the catalytic unit is inthe second temperature range, increasing the amount of reducing agentadded to the NOx reducing system at a second rate, said first rate beinghigher than said second rate, the first and second zeolite catalystsbeing metal-exchanged catalysts, and the first zeolite catalyst being acopper-exchanged zeolite catalyst and the second zeolite catalyst beingan iron-exchanged zeolite catalyst.
 12. The method of claim 11 whereinthe reducing agent is an ammoniagenic agent.